Urea silicon product and the preparation thereof

ABSTRACT

This invention relates to urea containing silicon compounds and the uses thereof, particularly as coupling agents on glass and to the similar use of substituted urea containing silicon compounds.

United States Patent Pepe et al. [4 1 June 20, 1972 [54] UREA SILICONPRODUCT AND THE [56] References Cited PREPARATION THEREOF UNITED STATESPATENTS 1 Inventors: Enrico J- p James Mmden, both of 2,907,782 10 1959Pike ..260/448.2 Amawalk, N.Y. 2,966,507 12/1960 Montgomery.....260/448.2 2,973,383 2/1961 Black ..260/448.2 [73] Carbide 3,033,8155/1962 Pike et al. ...260/448.2 x [22] Filed: Sept. 12, 1968 3,440,2614/1969 Saam ..260/448.2 3,208,971 9/1965 Gilkey et al.... ...260/448.8 X1 1 PP 759,524 3,478,075 11/1969 Jack et a1. ..260/448.8 x

Relaed Application Data Primary Examiner-Tobias E. Levow [63]Continuation-impart of Ser. NO. 729,895, May 17, Assisi! Examiner-wens"F l y 1968 abandoned Attorney-Paul A. Rose, Aldo .1. Cum, George A.Skoler and Eugene C. Trautlein [52] U.S. Cl ..260/448.8 R, 260/448.2 N,260/2 S, [57 ABSTRACT 260/38 260/348 Th1s 1nvent1on relates to ureacontaming s1l1con compounds [5 '3 Cl 7/02 Con 7/04 and the uses thereof,particularly as coupling agents on glass [58] Fleld of Search 260/448.8R, 448.2 N and to the similar use f Substituted urea containing siliconcompounds.

10 Claims, No Drawings wherein at least one of the three free valencesof the silicori atom are bonded directly to hydrolyzable groups such asa1- koxy, acyloxy, aryloxy, amino, and the like, and/or oxygen which inturn is bonded to other silicon atoms to form a siloxane. The remainingfree valences of the silicon atom are bonded by carbon to silicon bondsto monovalent organic groups. In the above formula I, R is an alkyleneradical containing at least three carbon atoms and at least 1 nitrogenatom therein bonded to each (H NCO-Q-tO form (HzNCON g I least one (1)free valence of is bonded to an alkylene carbon atoms of R, any otherfree valences thereof are bonded to either hydrogen, alkyl, aryl,cycloalkyl, aralkyl, and the like; any nitrogen in R is separated fromsilicon by at least three sequential carbon atoms; and n is at least 1and typically not greater than about 3.

Specifically illustrative of such urea substituted silicon compounds arethose depicted by the following formula: II

wherein R and n are described above, R is any monovalent organic groupbonded to silicon by a carbon to silicon bond and typically contains notmore than about 12 carbon atoms; R can be hydrogen and/or R; R ishydrolyzable and/or condensible radical such as hydroxyl, alkoxy,aryloxy, acyloxy and the like; R is hydrogen, alkyl aryl, acyl and thelike; m is or l;ais0,lor2;bis0,12or3;ois0orl;pisequalto3-a when m is 0,and when m is 1, is 0; and q is 0 whenp is equal to 3-11 and q is 0 or apositive number when m is 1.

Illustrative of R is any monovalent organic radical such as alkyl (e.g.,methyl, ethyl, pentyl, dodecyl, octadecyl, 2-ethylhexyl, and the like),cycloalkyl (such as cyclobutyl, cyclohexyl, 4-methylcyclohexyl, and thelike), aryl (such as phenyl, 2 naphthyl, Z-anthracyl, biphenyl, and thelike), alkaryl (such as 4-methylphenyl, 2,4-diethylphenyl,4-dodecylphenyl, and the like), aralkyl (such as phenylethyl), alkenyl(such as vinyl, allyl, S-butenyl, oleyl, and the like), alkadienyl (suchas l-butadienyl-l,4,l-octadecatrienyl-9, 11, 13-, l-neoprenyl, and thelike), cycloalkenyl (such as S-cyclohexenyl), haloalkyl (such aschloromethyl, gamma-chloropropyl, 3,3,3- trifluoropropyl,perfluoropropyl, haloaryl (such as 4- chlorophenyl, 2,4-dichlorophenyl,chloronaphthyl), halocycloalkyl (such as 4-chlorocyclohexyl), cyanoalkyl(such as beta-cyanoethyl, gamma-carboxypropyl and the like); cyanoaryl(such as 4cyanophenyl); cyanocycloalkyl (such as 4-cyanocyclohexyl,3-cyanocyclopentyl, and the like); carboxyalkyl (such asbeta-carboxyethyl, gamma-carboxypropyl, and the like); carboxyaryl (suchas 4-carboxyphenyl); carboxycycloalkyl (such as 4-carboxycyclohexyl,B-carboxycyclopentyl, and the like; isocyanatoalkyl (such asgammaicocyanatopropyl, delta-isocyanatobutyl, and the like);isocyanatoaryl (such as 4-isocyanatophenyl); isocyanatocycloalkyl (suchas 4-isocyanato-cyclohexyl); alkyl or aryl carboxyalkyl (such asbetamethylcarboxyethyl, gamma-phenyl carboxypropyl, and the like);hydroxyalkyl (such as hydroxymethyl, gamma-hydroxypropyl, and the like);hydroxy(polyalkyleneoxy)alkyl (such asomega-hydroxy(polyethyleneoxy)propyl, and the like); alkenoyloxyalkyl(such as gammaacrylyloxypropyl, gamma-methacryloxypropyl, and the like);epoxyalkyl (such as 1,2-epoxyethyl, 1,2-epoxypropyl, 1,2- epoxybutyl,and the like); epoxy alkyloxyalkyl (such as glycidyloxypropyl);epoxycycloalkyl (such as beta-3,4-epoxycyclohexylethyl); aminoaryl andaminoalkyl (such as aminomethyl, gamma-aminopropyl, delta-aminobutyl,paminophenyl, and the like); and the like.

Illustrative of alkoxy, acyloxy, aryloxy, amino, and the like, such asmentioned above and characterized by R or R when q is a positive number,are for example methoxy, ethoxy, propoxy, dodecyloxy, isopropoxy, andthe like; phenoxy, naphthyloxy, biphenyloxy, and the like, alkylaminoand arylamino (such as methylamino, diethylamino, phenylamino, and thelike), formyloxy, acetyloxy, proprioxy, and the like, anyorgano-functional radicals such as hydroxyalkoxy (such asbeta-hydroxyethoxy, gamma-hydroxypropoxy, and the like);hydroxyalkoxyalkoxy (such as beta-hydroxyethoxy-ethoxy,omega-hydroxy(polyethyleneoxy)ethoxy, omega-hydroxy(poly-1,2-propyleneoxy), and the like; cyanoalkoxy (such asbeta-cyanoethoxy, beta-cyanohexoxy and the like); cyanoalkoxyalkoxy(such as beta-cyanoethoxy, omega-cyanoethoxy (polyethyleneoxy)omega-cyanoethoxy(poly-1,2- propyleneoxy), and the like); carboxyalkoxy(such as betacarboxyethoxy, beta-carboxyhexoxy and the like); haloalkoxy(such as chloromethoxy, bromoethoxy perfluoropropoxy, and the like); andthe like.

The products of this invention may be produced by the treatment ofsilanes or siloxanes characterized by the following formula:

III

wherein R is a divalent alkylene radical of at least three carbon atomsand which separates the isocyanato group from silicon by at least threesequential carbon atoms; and R, R, R, R, n, m, a, b, 0, p, and q aredescribed above.

The treatment of the silanes or siloxanes characterized by formulae IIIand IV are different in order to make the ureas of formulae I and II.The amine of formula III is converted to urea by the reaction of thesilanes or siloxanes of formula III with an organocarbamate such asalkyl, cycloalkyl or aryl carbamates illustrated by methyl carbamate,ethyl carbamate, and n-propyl carbamate, n-butyl carbamate,cyclohexylcarbamate phenyl carbamate, 4-methylphenyl carbamate, 4-dodecyl phenyl carbamate, biphenyl carbamate; and alkylene,cycloalkylene and arylene carbamates, such as ethylene dicarbamate,1,4-butylene dicarbamate, 1,4-phenylene dicarbamate, 4,4'-bisphenylenedicarbamate, 1,4-cyclohexylene dicarbamate, and the like. The reactioncan be carried out neat or in solution or dispersion using solvents ornonsolvents for the silane and/or the carbamate reactants. Types ofsolvents and nonsolvents include water, hydrocarbon solvents, ethersolvents, amide solvents, ketone solvents and the like, such as mineralspirits, hexane, n-nonane, benzene, toluene, xylene, methylethyl ketone,methylisobutyl ketone, diethylether, di-n-diisopropyl ether,N,N,-dimethyl formamide, and the like. The temperature of the reactioncan be relatively low depending upon the reactivity of the carbamate andthe amount of amine present in the reaction, usually temperatures in therange of about 40 C. to about 180 C. are satisfactory. Typically atemperature about 50 C. to about 150 C. is more desirable.

This reaction can be operated under atmospheric or subatmosphericpressures. Superatmospheric pressures are employable but are notconsidered to operate as beneficially as subatmospheric and atmosphericpressures. The reaction product can be separated by distillation,crystallization, decantation, and the like, utilizing standardprocessing equipment and procedures.

The treatment of an isocyanato silicon compounds of formula IV toproduce the urea involves the reaction of ammonia with the isocyanate.This reaction can proceed at exceedingly low temperatures, viz., as lowas -75 C., or lower, typically at least 50 C., and usually not greaterthan about 150 C. The reaction alsocan be performed neat or in admixtureeither by dissolution or suspension of either one or both of thereactants in a solvent or nonsolvent, as the case may be. Usually, theisocyanate of formula IV is liquid, most desirably in solution, andtheammonia is bubbled through the solution as a gas or is employed inliquid form. In the preferred process, the isocyanate is reacted withliquid ammonia. This minimizes the use of superatmospheric pressure asis required when using gaseous ammonia.

This invention also contemplates a number of other embodiments,particularly the utilities of the aforementioned ureas as well as ureascharacterized by the following formula:

v 112ml ,,-RSi(O (Ran ammo,

'ifiTreln R, R, R, R, R 375, b, m, o, p, and q, are described above, andR may be alkyl or aryl, such as described above, provided at least one Ris hydrogen or methylol, or both Rs maybe methylol, i.e., (ClI,0I-I).These materials may be formed by reacting the product of formula II withan alkyl or aryl halide to add one alkyl or aryl group or by reactingaryl or alkyl amines with the isocyanate of formula IV or by reactingN-alkyl or N-aryl carbamate esters with the amine of formula III. Themethylol substituted ureas may be formed by simple dissolution ordispersion of silanes or siloxanes characterized by formula II inaqueousformaldehyde solution, or by direct reaction of formaldehyde orits precursors, to wit, hexamethylenetetraamine or trioxane inanon-aqueous solvent solution of the silane or siloxane. Conventional artrecognized reaction conditions may be employed.

The amines which may be treated in accordance with the process of thisinvention are those which are described in U.S. Pat. No. 2,971,864,patented Feb. 14, 1961, specific embodiments being illustrated inexamples 1, 2, 3, 4 and 6 thereof; US. Pat. No. 2,832,754, particularlyat Examples 1, 2, 3 and 4 thereof; and US. Pat. No. 2,942,019 at columnsI, 2, 3 to lines 17 of column 4 with respect to silanes and siloxanehomopolymers and copolymers which are described therein to be reactedwith aldehydes and ketones.

It has been found that the above ureas, used as aqueous solutions of thehydrolyzates of the aforedescribed urea substituted silanes of formulasII and V, or the partially condensed to totally condensed siloxanes offormulas II and V employed neat or in solution, can be most effectivecoupling agents, particularly on fiber glass for further reaction with abroad variety of thermosetting and/or thermoplastic resins. They can beadded first onto the glass followed by treatment with the resin or theycan be premixed with the resin and added to glass. In any event, it isfound that those silanes and siloxanes supplied to the glass surface toform a siloxane coated thereon act to strongly adhere resin eithersimultaneously or thereafter supplied to the glass. Illustrative ofresins which can be effectively bonded include the thermosetting resins,such as the phenol formaldehyde, melamine-femaldehyde, polyester resins,such as those formed by the reaction of ethylene glycol, maleic acid oranhydride with or without styrene monomer and/or polymer, alkyd resins,polyurethane resins, epoxy resins, and the like. It may also be used tocouple thermoplastic resins which possess reactive groups, such asisocyanate, carboxy, epoxy, and the like, by the inclusion in the resinof a catalyst for enhancing the reaction such as the well known metalcatalysts, e.g., tin octoates, alkyl tin compounds, lead, cobalt,manganese, zinc, titanate and the like, driers and catalysts to enhancethe reaction to the urea siloxane with the resin on the glass fibersurface. Also there may be included in the resins peroxide andhydroperoxide catalysts for the resins to achieve theoretical formationof fragments from the urea siloxanes on the glass surface which add tothe resin and vice versus. Resins which most suitably respond to thistype of reaction system include the thermoplastics, such as polyethene,polypropylene, copolymers of ethylene and propene, polyvinylchloride,polyvinylbutyral, polyacrylonitrile, copolymers of styrene andacrylonitrile, copolymers of styrene and butadienel,3, copolymers ofacrylonitrile and vinylchloride, and the like. The invention isparticularly useful in this area in enhancing the bonding ofpolyvinylbutyral resin to plate glass in the manufacture of plate glasslaminates. The urea substituted siloxanes also act as effective couplingagents on other inorganic substrates such as siliceous pigments andfillers, e.g., clay, silica, hydrated silica, fumed silica, sand and thelike. The silanes-are most effectively employedin treating sand whichcan be employed in foundry molding using hot or cold curing resins ofthe phenolformaldehyde, resorcinol-formaldehyde, andmelamine-formaldehyde type. These ureas substituted siloxanes enhancethe bonding of the resin to the sand.

EXAMPLE 1 in near quantitative yields.

Infrared spectral survey is in agreement with the assignedmonosubstituted urea structure. calc for C,H SiO N,- 37.8% C; 8.2% H;12.6% Si; 12.6% N; 41.9% OMe. Anal. 38.1, 8.1, 12.7, 12.2, 39.6.

b. Transesterfication Method Into a 500 m. distillation flask outfittedwith thermometer and attached to a 1 distillation Vigreaux column,distillation head and receiver is charged 110.5 gms. (0.5 moles) of'y-NH2(OHz)sSl(OEt) 44.5 gms. (0.5 mole) of CHaQIlzIgQiE IEIIT A iv 7and 250 ml. of toluene. Titration of the total mixture in isopropylalcohol, using standardized 0.1N HCl and brom cresol green indicator,shows the presence of 1.71 meg. of NI-I per ml. The reaction mixture isheated to reflux at 130 C. while removing 5 ml. of distillate boiling atfrom to 1 10 C. at atmospheric pressure over 1 hour. Retitration of thetotal reaction mixture indicates 1.64 meg/ml. of NH,. At this point, 0.5gms. of dibutyltin oxide is added and reflux continues for 3 hoursduring which time 186 gms. of a 83 percent toluene 45.1% EtOH(ethanol)mixture is removed at the head, boiling at from 105 to C. at atmosphericpressure. Removal of the balance of toluene and ethanol by vacuum use ofsilane as set forth in the table:

stripping to 100 C. at 1 mm. mercury pressure produces 13 8.4 gms. 104weight percent of calculated yield) of crude containing 0.03 meg/ml. ofresidual NH (94 mole percent conversion). Infrared spectral surveyverifies the presence of monosubstituted urea structure. Aside from theexpected differences due to triethoxysilicon groups, the majorabsorption characteristics are identical to those obtained from theproduct of Example la.

EXAMPLE 2 Composites were prepared as-follows: 500 grams of glass beadsrange in sizes from 325 to 40 mesh, US. Standard, are mixed with 30.9grams of a 50 per cent aqueous solution of mcthylol rich A-stagephenol-formaldehyde resin (approximately 3 weight per cent resin solidsbased on weight of glass lwudu). 0.9 grunt of concentrated uqucounNl-LOH solution, 7.7 grams of water und 0.0l6 grams ol'nllune (0.1weight per cenl sllane based on resin solids). thin mixture is placed ina multiple cavity dumbbell shaped mold and cured for 7 min. at

450 F. to produce a cured article of the mold shape.

The following table shows tensile strengths of a number of such moldedarticles, the differences between each being the TENSILE STRENGTHRESULTS 1 Produced according to the following reaction:

3 Produced according to the following reaction:

3 Produced according to the following reaction:

(CH50)aSi(CH2)BN=C=-O+NH(CHa)2 0 (GHaOMSi(CH2)aNH N(CH9)2 Into a3-liter, 3-necked flask outfitted with thermometen,

heating mantle, mechanical stirrer and a 12 inch Vigreaux gms. 5.0moles) of NH (CH NH(CH Si(OMe) 375 gms.

hydrous toluene and 3.9 gms. (0.25 wgt percent) of dibutyl tin oxide.The stirred mixture is heated at reflux from 96 to 1 19 C for 5 hours,during which time 751.9 gms. of distillate is removed boiling at from 64to 109 C at atmospheric pressure and determined by gas chromatographicanalysis to contain approximately 24 volume percent methanol and 76volume is removed and stripped under vacuum to 100 C at 1 mm. of mercurypressure to produce 605 gms. 2.28 moles) of (CH2 )2NH (cumsi (OMc)a in9! mole percent yield.

EXAMPLE 4 1 To 605 grams (2.28 moles) of O I lenaeerraeeaewas.

dissolved in 1,400 gms. of toluene is added an additional 187.5

- gms. (2.5 moles) of methyl urethane and the procedure described aboveis repeated to produce 668 gms. (2.17 moles) of light yellow, highviscosity 0 Nlln NllfllllshNd Nllz) (UllmN((HhhBKUMo);

in 95.4 mole percent yield.

EXAMPLE 5 In much the same manner as described in Example 3, 590 gms.(6.0 moles) of NH (CH NH(CH NH(CH Si(OMe) is reacted with 450 gms. (6.0moles) of lMeOOCNl-l until 6 moles of by-product methanol has beenformed and removedby distillation. One third of the total ,reactionmixture is removed and vacuum stripped to 100 .C/ 1.0 mm. to obtain615.6 gms.(2.0 moles) of the mono-urea derivative,

401a light yellow viscous syrup soluble in water, alcohols and toluene.

EXAMPLE 6 To the remaining 4 moles of mono-urea derivative obtained inExample 5 is added 300 gms., 4.0 moles of additional MeOOCNH- 1 liter oftoluene and the process of methanol removal described above repeateduntil an additional 4 moles of methanol is formed and removed. The crudereaction mixture is divided in half and isolation of the diureaderivative accomplished as described above. There results 643 gms. 1.83moles) of thermoplastic light orange, glass-like (at room temperature,25 C.) di-urea derivative,

0 0 NHn NH(CH2)2N( NH2) (CH2) 3S1 (OMe);

which is soluble in methanol, ethanol, isopropanol, water and toluene.

EXAMPLE 7 To the remaining di-urea derivative prepared in Example 6 isadded 150 gms. (2.0 moles) of MeOOCNl-l 500 ml of addi- I 2 tionaltoluene and the transesterification reaction driven to column withdistillation head and receiver is charged 1,100:

completion in the same manner as described above. There results uponworkup in the aforementioned manner a quantitative yield of the tri-ureaderivative,

The latter is amine free, thermoplastic, clear orange, glasspercenttoluene. Exactly one half of the total reaction mixture hl e atroonitemperature and softensandflowsat about C.

and'is soluble in alcohols (eg. methanol, ethanol, etc.) and water.

As noted above, the urea silanes are extremely effective coupling agentsand are notably useful in coupling or enhancing the bonding of fiberglass to a plurality of organic materials such as rubber, e.g.,ethylene-propylene terpolymer rubbers R-SiE wherein at least one of theindividual free Si valences are bonded directly to a hydrolyzable group,selected from the group consisting of alkoxy, acyloxy, aryloxy, aminoand haloalkoxy, or oxygen which in turn is bonded to another siliconatom to form therewith a siloxane, and the remaining free valences arebonded by carbon to silicon bonds to monovalent organic groups selectedfrom the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl,alkenyl, alkadienyl, cycloalkenyl, haloalkyl, halocycloalkyl,cyanoalkyl, cyanoaryl, cyanocy'cloalkyl, carboxy-alkyl, carboxyaryl,carboxycycloalkyl, isocyanatoaryl, isocyana-tocycloalkyl, alkylcarboxyalkyl, aryl carboxyalkyl, hydroxyalkyl, hydroxy(polyalkyleneoxy)alkyl, alkenoyloxyalkyl, epoxyalkyl, epoxy alkyloxyalkyl, aminoaryl andaminoalkyl, R is a nitrogen containing alkylene radical containing atleast three carbon atoms and at least one nitrogen a es! the is drqastuflm q rw .v

is bonded to a member selected from the group consisting of hydrogen,alkyl, aryl, cycloalkyl and aralkyl, any nitrogen atom in R is separatedfrom silicon by at least three sequentially joined carbon atoms, and nis at least one.

2. The novel silicon compound of claim 1 wherein the radical forms partof the compound having the formula:

wherein R and n have the meaning described in claim I; R is a monovalentorganic group bonded to silicon by a carbon to silicon bond, selectedfrom the group consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl,alkenyl, alkadienyl, cycloalkenyl, haloalkyl, halocycloalkyl,cyanoalkyl, cyanoaryl, cyanocycloalkyl, carboxyalkyl, carboxyaryl,carboxycycloalkyl, isocyanatoaryl, isocyanatocycloalkyl, alkylcarboxyalkyl, aryl carboxyalkyl, hydroxyalkyl,hydroxy(polyalkyleneoxy)alkyl, alkenoyloxyalkyl, epoxyalkyl, epoxyalkyloxyalkyl, aminoaryl and aminoalkyl; each R is hydrogen or R; R is ahydrolyzable or condensible radical, selected from the group consistingof hydroxyl, alkoxy, acyloxy, aryloxy, amino and haloalkoxy; R is amember selected from the group consisting ohydroggn alky l, aryl andacyl; rn is or 1; a is 0, l or 2; b is 0,1, 2 or 3; o is 1; p is equalto 3-a when m is 0, and when m is l, p is 0; and'q is 0 when p is equalto 3-a and q is 0 or a posi tive number when m is l.

3. The process of producing urea substituted silicon compounds whichcomprises reacting a carbamate with an amino group of anaminoorganosilicon compound having the formula:

wherein R, R, R, R, R, n, m, a, b, o,p,,and q have the meaning describedin claim 2.

9. mN-dNmcHmmdNm) (omnumcnmsuocm 1 (CH2)aSl(OCHa)3

2. The novel silicon compound of claim 1 wherein the radical forms partof the compound having the formula: wherein R and n have the meaningdescribed in claim 1; R1 Is a monovalent organic group bonded to siliconby a carbon to silicon bond, selected from the group consisting ofalkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, alkadienyl,cycloalkenyl, haloalkyl, halocycloalkyl, cyanoalkyl, cyanoaryl,cyanocycloalkyl, carboxyalkyl, carboxyaryl, carboxycycloalkyl,isocyanatoaryl, isocyanatocycloalkyl, alkyl carboxyalkyl, arylcarboxyalkyl, hydroxyalkyl, hydroxy(polyalkyleneoxy)alkyl,alkenoyloxyalkyl, epoxyalkyl, epoxy alkyloxyalkyl, aminoaryl andaminoalkyl; each R2 is hydrogen or R1; R3 is a hydrolyzable orcondensible radical, selected from the group consisting of hydroxyl,alkoxy, acyloxy, aryloxy, amino and haloalkoxy; R4 is a member selectedfrom the group consisting of hydrogen, alkyl, aryl and acyl; m is 0 or1; a is 0, 1 or 2; b is 0, 1, 2 or 3; o is 1; p is equal to 3-a when mis 0, and when m is 1, p is 0; and q is 0 when p is equal to 3-a and qis 0 or a positive number when m is
 1. 3. The process of producing ureasubstituted silicon compounds which comprises reacting a carbamate withan amino group of an aminoorganosilicon compound having the formula:wherein R, R1, R2, R3, R4, n, m, a, b, o, p, and q have the meaningdescribed in claim 2.